Pyridines geometry

Other rate processes studied include isopropyl group rotation, (529) restricted rotations in phosphine derivatives of cyclopentadienyl complexes of iron and nickel, (530) and ring and nitrogen inversion in (en) complexes of praseodymium. (531) Molecular geometries of molecules in solution can be accurately determined from NMR spectra of the molecules oriented in a nematic phase of a liquid crystalline solvent. The effect of Eu(dpm), on the nematic phase spectrum of pyridine has been examined. The pyridine geometry is unaffected by the LSR. The observed LIS values can be separated into isotropic and anisotropic components. (532)... 

The direct coupling constants (A/) of pyridine, obtained from a spectrum of the molecule in a nematic liquid crystal solvent, are listed in Batterham s monograph (B-73NMR, p. lo). These data provide information about the geometry of the molecule, as the couplings are proportional to the inverse cube of the distance (r,/) between the nuclei. 

SF4 is unusual in apparently acting both as an electron-pair acceptor and an electron-pair donor (amphoteric Lewis acid-base). Thus pyridine forms a stable 1 1 adduct C5H5NSF4 which presumably has a pseudooctahedral (square-pyramidal) geometry. Likewise CsF (at 125°) and Me4NF (at —20°) form CsSFs and [NMe4]+[SFs] (Fig. 15.21a). By contrast, SF4 behaves as a donor to form 1 1 adducts with many Lewis acids the stability decreases in the sequence SbFs > AsFs > IrFs > BF3 > PF5 > ASF3. In view of the discussion on... 

Let s now look at an ab initio CIS calculation on pyridine. As a routine first step, I optimized the molecular geometry (yet to be discussed) at the HF/6-31G level of theory. It is interesting to examine the ab initio orbital configuration (Figure 11.3). 

Basis set dependence is important. The results in Table 16.1 were obtained for HF-LCAO calculations on pyridine. In each case, the geometry was optimized As a general rule, ab initio HF-LCAO calculations with small basis sets tend to underestimate the dipole moment, whilst extended basis sets overestimate it A treatment of electron correlation usually brings better agreement with experiment. 

The triplet nitrenium ion, however, lacks symmetry but, unlike the excited triplet states of other azaaromatic systems such as pyridine, is surprisingly planar.283 Theoretical dipole moments for cyclopent[c]- and cyclopent[rf]azepine, and the molecular geometry of cyclopent[rf]-azepine, have been calculated using semiempirical ab initio methods.3... 

The formation of an intramolecular H-bond is supported by the slower rate of amide proton exchange in pyridine/10% CD3OD. The influence of the stereochemistry on turn formation and turn geometry has been investigated. Seebach and coworkers have demonstrated that dipeptide sequences consisting... 

An /n-geometry can be ensured by appropriate substitution of the building block which carries the acid-base functionality, for instance by using 2,6-disubstituted aromatic compounds like pyridines, 2,6-disubstituted benzoic acids or other 2,6-disubstituted phenyl derivatives (see Scheme 1). The use of 2,6-disubstituted arenes is sometimes called the 1,3-xylyl trick and assures an intra-annular orientation. 

With its empty 3 d orbitals, SF4 also acts as a Lewis acid. This molecule forms adducts with pyridine and with fluoride ion. Each adduct has square pyramidal geometry, with a lone pair of electrons completing an octahedral... 

The ligand group can be introduced either on the meso or on the /5-pyrrole position of the porphyrin ring, but the synthesis of the meso-functionalized derivatives is easier and has been more widely exploited. Balch (50-53) reported that the insertion of trivalent ions such as Fe(III) (32) and Mn(III) (33) into octaethyl porphyrins functionalized at one meso position with a hydroxy group (oxophlorins) leads to the formation of a dimeric head-to-tail complex in solution (Fig. 11a) (50,51). An X-ray crystal structure was obtained for the analogous In(III) complex (34), and this confirmed the head-to-tail geometry that the authors inferred for the other dimers in solution (53) (Fig. lib). The dimers are stable in chloroform but open on addition of protic acids or pyridine (52). The Fe(III) octaethyloxophlorin dimer (52) is easily oxidized by silver salts. The one-electron oxidation is more favorable than for the corresponding monomer or p-oxo dimer, presumably because of the close interaction of the 7r-systems in the self-assembled dimer. 

In pyridine- X-C interactions, the C - X moiety is roughly coplanar with the pyridine and the two C-N- X angles are approximately 120° [129,143, 144]. The same holds for other nitrogen heteroaromatics (e.g. pyrazine, quinoline, etc.) [145-147]. A carbonyl group pins the donors after a trigonal planar geometry and works either as a mono- [148,149] or bidentate XB acceptor [150]. Sulfoxides behave similarly [151,152] and imines form XB along the expected axis of the lone pair [153]. 

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